Fungicidal carbamaldoximes

ABSTRACT

Novel carbamaldoximes of the formula   WHEREIN Y is selected from the group consisting of hydrogen, chlorine and bromine and X is selected from the group consisting of phenyl optionally substituted with at least one member of the group consisting of halogen, cyano, -NO2, alkyl of 1 to 6 carbon atoms and alkoxy of 1 to 6 carbon atoms and nitrofuryl having fungicidal activity.

li lihlfil are O United State: [111 3,887,711 erronnet et. a1. 45 Jun 3, 1975 FUNGICIDAL CARBAMALDOXIMES 3,553,264 1/1971 Addor 260/566 AC [75] Inventors: Jacques Perronnet; Pierre Girault,

both f Paris, France Przmary Examiner-V. D. Turner Arron ,A t,0 F H [73] Assignee: Roussel Uclaf, Paris, France r ey gen r amm0nd& Lmen [22] Filed: June 26, 1974 57 ABSTRACT PP 483,290 Novel carbamaldoximes of the formula Related U.S. Application Data [62] Division of Ser. No. 408,744, Oct. 23, 1973, Pat. N0. 0

XC=N--0-C'--NH-C=CC1 I [30] Foreign Application Priority Data 1 Nov 6, 1972 France 72.39141 52 U.S. Cl. 424/300; 424/298; 424/327; wherein Y is Selected from the group consisting of y- 106/15 drogen, chlorine and bromine and X is selected from 51 Int. Cl A0ln 9/20 h group Consisting of p y Optionally Substituted 581 Field of Search 424/300, 298, 327 Wlth at least one member of the group consisting of halogen, cyano, NO alkyl of 1 to 6 carbon atoms 5 References Cited and alkoxy of l to carbon atoms and nitrofuryl hav- UNITED STATES PATENTS mg fungicidal activity.

3,223,733 12/1965 Heiss et al 260/566 AC 3 Claims, No Drawings FUNGICIDAL CARBAMALAOYIMES This is a continuation, division of Ser. No. 408,744, filed Oct. 23, 1973 now US. Pat. No. 3,836,582.

STATE OF THE ART US. Pat. No. 3,742,036 describes aldoximes of the formula wherein R and R are lower alkyl and R is hydrogen or lower alkyl having biocidal, fungicidal or bactericidal properties but these are chemically distinct from the compounds of formula I.

OBJECTS OF THE INVENTION It is an object of the invention to provide the novel carbamaldoximes of formula I and a process for their preparation.

It is another object of the invention to provide novel fungicidal compositions and to provide a novel method of combatting fungi.

These and other objects and advantages of the inventron will become obvious from the following detailed description.

THE INVENTION The novel carbamaldoximes of the invention have the formula wherein X and Y have the above definition. The reactron is preferably effected in the presence of an organic solvent such as toluene r tetrahydrofuran and a tertiary base such as triethylamine or pyridine.

The aldoximes of formula II can be prepared by known methods such as condensing hydroxylamine with the appropriate aldehyde.

The novel fungicidal compositions of the invention are comprised of an effective amount of at least one compound of formula I and a carrier. The compositions can also optionally contain one or more other pesticides or other products influencing the growth of plants.

The compositions may be in the form of powders, granules, suspensions, emulsions or solutions, containing besides the active ingredients, cationic, non-ionic or anionic surface active agents; inert powders such as talc, clays, silicates, Kieselguhr, etc.; or a vehicle such as water, alcohol, hydrocarbons or other organic solvents, mineral, vegetable or animal oils, etc.

The fungicidal powders used for foliar spraying preferably contain 25 to 95% by weight of the compounds of formula I and the fungicidal compositions used as foliar powders preferably contain 2.5 to 99% by weight of the compounds of formula I.

An example of a composition for a foliar spray comprises 25% by weight of O-[N- trichlorovinylcarbamoyl]-04,pdichlorobenzaldoxime, 15% by weight of Ekapersol S (condensation product of sodium naphthalene sulfonate), 0.5% by weight of Brecolane NVA (sodium alkyl naphthalene sulfonate), 34.5% by weight of Zeosil 39 (precipitated synthetic hydrated silica) and 25% by weight of Vercoryl S (colloidal Kaolin).

For the protection of paints against fungi, the active compound of formula I may be incorporated during grinding of the pigments. The concentration of the products of formula I is preferably 0.05 to 5% by weight of the paint. For example, 1% by weight of O- [N-trichlorovinylcarbamoyl]-a,pdichlorobenzaldoxime is added to the pigments during grinding to obtain a paint protected against fungi.

The novel method of the invention for killing fungi comprises contacting fungi with a fungicidal amount of at least one compound of formula I. The method is useful in agriculture and in protecting paints.

In the following examples there are described several preferred embodiments to illustrate the invention. However, it should be understood that the invention is not intended to be limited to the specific embodiments.

. EXAMPLE 1 O[N-trichlorovinylcarbamoyl]-a,pdichlorobenzaldoxime 19 g of a,p-dichlorobenzaldoxime [Farley, Proc. N. Dakota Acad. Sci., Vol. 13 (1959), p. 61] and 20 g of trichlorovinyl isocyanate (US. Pat. No. 3,468,923) were added to ml of toluene and the mixture was stirred for 30 minutes at C. The toluene was re moved by distillation under reduced pressure and the residue was added to petroleum ether (boiling point-65-75C) containing 10% isopropyl ether. The crystals formed were recovered by vacuum filtration and dried to obtain 27.2 g of O-[N- trichlorovinylcarbamoyl 'a,p-dichlorobenzaldoxime melting at 92C.

Analysis: c,,,H .c| .N.o Calcd: C 33.14 70 H 1.39 Cl 48.92 N 7.73 Found: 33.3 1.8 48.5 7.5

EXAMPLE 11 Calcd: C 29.25 H 1.22 7 N 12.79 Cl 32.38 Found: 29.3 1.1 12.5 32.3

EXAMPLE III The protective activity of O-[N- trichlorovinylcarbamoyl]-a,p-dichlorobenzaldoxime for paints against fungi comprised incorporating 10 ml of an acetone solution of the test compound into 100 g of paint (oil or water base paint) to obtain a concencompound. Layers of paint were prepared by spreading the paint thus treated on polyethylene sheets while the control layers were untreated. After drying at 24 to 48 hours, the paint layers were removed from the polyethylene and were cut into 5 X 2 cm pieces. The said test pieces of paint were placed in dishes containing a gelose nutritive medium free from assimilable carbon and comprised of 3 g of ammonium nitrate, 0.5 g of magnesium sulfate, 0.25 g of potassium chloride, 1 g of monopotassium phosphate, g of agaragar and 1,000 g of demineralised water. Before addition of agar-agar, the

pH was adjusted to 67. Each dish contained 2 test pieces and 4 tests were run for each concentration.

The test pieces were contaminated by placing on 15 each test piece drops of a fungi spore suspension of Penicillium luteum, Myrot/zecium verrucaria, Cladosporium herbarum, Stachybotrys atra, Paecylomyces Varioti, Pullularia pullulans, Tricltoderma lignorum, Chaetamium globosum and Aspergillus niger. The samples were stored in a tropical room at C and relative humidity for 3 months. The attack before washing and after washing (developments above all samples, developments by placement of drops; stains at the placement of the drops, no attack) was noted. The washing 25 was for the purpose of eliminating the stains caused by superficial development of mould, which do not corre spond to an effective attack of the paint. The results of the following Tables show that the test compound has a good activity for protecting paints against the various tration of 2, 1, 0.5 or 0.25% by weight of the active 0 ld d,

STACHYBOTRYS ATRA before washing WATER BASE PAINT OIL-BASE PAINT after washing before washing after washing Concentrations MA 2 l 0,5 0,25 2 1 0,5 0,25 2 l 0,5 0,25 2 1 0,5 0,25

Developement over all the test piece Developement at the placement of the drops Stains at the placement of the drops TOTAL PROTECTION PAECYLOMYCES VARIOTI WATER BASE PAINT OIL-BASE PAINT before painting after washing before washing after washing Concentrations MA 2 l 0,5 0,25 2 l 0,5 0,25 2 1 0,5 0,25 2 l 0,5 0,25

Developement over all the test piece Developement at the placement of the drops Stains at the placement of the drops TOTAL PROTECTlON PULLULARIA PULLULANS WATER BASE PAINT OIL-BASE PAINT before washing after washing before washing after washing Concentrations MA 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25

Developement over all the test piece Developement at the placement of the drops Stains at the placement of the drops TOTAL PROTECTION TRlCHODERMA LIGNORIUM WATER BASE PAINT OIL-BASE PAINT before washing after washing before washing after washing Concentrations MA 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25

Developement over all the test piece Developement at the placement of the drops Stains at the placement of the drops TOTAL PROTECTION CHAETOMIUM GLOBOSUM before washing WATER BASE PAINT OIL-BASE PAINT after washing before washing after washing Concentrations MA 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25 2 'l 0,5 0,25

Developement over all the test piece Developement at the placement of the drops Stains at the placement of the drops TOTAL PROTECTION ASPERGILLUS NIGER WATER BASE PAINT OIL-BASE PAINT before washing after washing before washing after washing Concentrations MA 2 1 0,5 0,25 2 1 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25

Developement over all the test piece Developement at the placement of the drops Stains at the placement of the drops TOTAL PROTECTION PENlClLLlUM LUTEUM WATER BASE PAINT OIL-BASE PAINT before washing after washing before washing after washing Concentrations MA 2 l 0,5 0,25 2 I 0,5 0,25 2 l 0,5 0,25 2 I 0,5 0,25

Developement over all the test piece Developement at the placement of the drops Stains at the placement of the drops TOTAL PROTECTION MYROTHECIUM VERRUCARIA WATER BASE PAINT OIL-BASE PAINT before washing after washing before washing after washing Concentrations MA 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25 2 I 0,5 0,25

Developement over all the test piece Developement at the placement of the drops Stains at the placement of the dro ps TOTAL PROTECTION CLADOSPORIUM HERBARUM before washing WATER BASE PAINT OlL-BASE PAINT after washing before washing after washing Concentrations MA 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25

Developement over all the test piece Developement at the placement of the drops Stains at the placement of the drops TOTAL PROTECTION Various modifications of the products and methods atoms and alkoxy of 1 to 6 carbon atoms; and a carrier. of the invention may be made without departing from 2. A method of killing fungi comprising contacting the spirit or scope thereof and it should be understood fungi with a fungicidal amount of a compound of the that the invention is to be limited only as defined in the formula appended claims.

We claim: 0 l. A fungicidal composition comprising an effective ll amount of a compound of the formula 1 I Y Cl i l wherein Y is selected from the group consisting of hy- X"C=N"O'C NH-C|:=FCl2 drogen, chlorine and bromine and X is selected from C1 the group consisting of phenyl optionally substituted with at least one member selected from the group conwherein Y is selected from the group consisting of hysltstmg g l z jgs g to 6 Carbon drogen, chlorine and bromine and X is selected from a g l g a 2 wherein theactive com the group consisting of phenyl optionally substituted d e 0 z FNitriChIOrOVin lcarbamo H with at least one member selected from the group congi i y y sisting of halogen, cyano, -NO alkyl of l to 6 carbon 

1. A FUNGICIDAL COPOSITION COMPRISING AN EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
 1. A fungicidal composition comprising an effective amount of a compound of the formula
 2. A method of killing fungi comprising contacting fungi with a fungicidal amount of a compound of the formula 